CN104610786A - Novel environment-friendly process for producing carbon black - Google Patents
Novel environment-friendly process for producing carbon black Download PDFInfo
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- CN104610786A CN104610786A CN201510060162.9A CN201510060162A CN104610786A CN 104610786 A CN104610786 A CN 104610786A CN 201510060162 A CN201510060162 A CN 201510060162A CN 104610786 A CN104610786 A CN 104610786A
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Abstract
The invention relates a novel environment-friendly process for producing carbon black, in particular to a tail gas denitrification process in a carbon black production process. A reaction device, a preheating device and a prilling granulator need to be utilized, wherein the reaction device comprises a reaction furnace, a choke, a reaction chamber and a cooling zone, the preheating device comprises an air preheater and an oil preheater, the prilling granulator comprises a carbon black classification device, a grilling granulating device and a drying device, and the drying device comprises a drying room and a tail gas passage. The novel process mainly comprises four steps of pyrolysis of raw oil, quenching of carbon black smoke, preheating of air and oil by high-temperature carbon black smoke, separation of carbon black smoke and denitrification process on tail gas. Compared with the prior art, the process has the advantages that the tail gas can be subjected to denitrification process during a drying stage of carbon black particles, meanwhile, the drying of the carbon black particles is not influenced, the nitrogen oxide in the tail gas is converted into nitrogen, and pollutants in the tail gas are reduced.
Description
Technical field
The present invention relates to a kind of manufacturing process of carbon black, particularly relate to tail gas denitrification process in a kind of carbon black process.
Background technology
Light, the pine of carbon black to be a kind of main component be decolorizing carbon and superfine black powder, surface-area is very large, scope, from 10-3000m2/g, is the product (having larger adhesivity) that organism (Sweet natural gas, heavy oil, fuel wet goods) obtains through incomplete combustion or decomposes under the condition of lack of air.The Application Areas of carbon black widely, can make black dyes, for the manufacture of ink stick, ink, paint etc., also for cooking the strengthening agent of rubber, has important effect at industrial circle.Traditionally, in manufacturing technologies of carbon black flow process, air and fuel burn in Reaktionsofen, and raw material sprays in burned flame after atomization, generate carbon black through high temperature pyrolysis.Carbon black is suspended in combustion gas and forms flue gas.Flue gas send air preheater after chilling, oil preheater is lowered the temperature further, and the flue gas after air preheater cooling can send into bag filter again after the cooling of postorder interchanger, and isolated carbon black delivers to granulation in tablets press, then dry in drying machine.Tail gas can be produced, containing great amount of carbon dioxide, a small amount of methane, oxynitride, sulfide in tail gas, and containing not collecting the carbon powder dust got off, if directly discharge will cause serious environmental pollution in the manufacturing processed of carbon black.So present most enterprise all can to the in addition recycle of tail gas profit, current carbon black tail gas has three kinds of main applications: one is be equipped with tail gas boiler for generating; Two is arrange quenching boiler and waste heat boiler, sells steam; Three is sell carbon black tail gas, supply local resident town gas.Substantially all when carbon black manufactures can carry out desulfurization process to tail gas and not carry out denitrogenation processing, and the detrimental effect of oxynitride to environment is very big, it is one of essential substance forming acid rain, also be form the important substance of photo-chemical smog in air and consume an important factor of O3, oxynitride all has toxicity in various degree simultaneously.
Summary of the invention
The present invention is directed to deficiency of the prior art, provide a kind of novel environment friendly technique of producing carbon black, denitrogenation processing can be carried out to tail gas at the drying stage of carbon black pellet, do not affect the drying of carbon black pellet simultaneously, make the conversion of nitrogen oxides in tail gas be nitrogen, reduce the pollution substance in tail gas.
In order to solve the problems of the technologies described above, the present invention is solved by following technical proposals, a kind of novel environment friendly technique of producing carbon black, need to utilize reaction unit, primary heater unit and prilling granulator, reaction unit comprises Reaktionsofen, trunnion, reaction chamber and cooling section, primary heater unit comprises air preheater and oil preheater, prilling granulator comprises carbon black grading device, prilling granulator and drying installation, it is characterized in that comprising following step: steps A): the high temperature air that temperature reaches 750 DEG C to 900 DEG C after preheating reacts with the combustion oil after preheating and mixes in Reaktionsofen, burning, produce the hot combustion gas stream of temperature between 1700 DEG C to 2010 DEG C, hot combustion gas stream flows into and in trunnion, to spray into temperature after trunnion between 170 DEG C to 190 DEG C and the stock oil of atomization, stock oil mixes with hot combustion gas stream at reaction furnace chamber, rapid cracking, produce carbon black smoke, step B): carbon black smoke, after entering cooling section, sprays water coolant in cooling section, and carbon black smoke temperature after over-quenching drops to 950 DEG C, step C): carbon black smoke after leaving from cooling section successively to air preheater and oil preheater, step D): carbon black smoke makes carbon black smoke be separated into carbon black powder and high-temperature tail gas from entering carbon black grading device after oil preheater leaves, carbon black powder becomes carbon black pellet after prilling granulator, after carbon black pellet puts into the kiln of drying installation, high-temperature tail gas enters the kiln of drying installation simultaneously and flows to tail gas air flue, the drying temperature of kiln when drying, between 1000 DEG C to 1200 DEG C, adds nitrogen reductant when high-temperature tail gas cools to 950 DEG C in tail gas air flue in tail gas air flue.
In technique scheme, preferably, described nitrogen reductant comprises ammoniacal liquor, urea and bicarbonate of ammonia.
In technique scheme, preferably, in described step D, the described nitrogen reductant sprayed in cooling section is described ammoniacal liquor, and it is the ratio of 1.5 that described ammoniacal liquor follows ammonia nitrogen mol ratio (NSR) when adding.
In technique scheme, preferably, in described step D, the described nitrogen reductant sprayed in cooling section is the mixture of described ammoniacal liquor and described bicarbonate of ammonia, it is the ratio of 1.5 that described ammoniacal liquor follows ammonia nitrogen mol ratio (NSR) when adding, and it is the ratio of 2 to 2.5 that described bicarbonate of ammonia follows ammonia nitrogen mol ratio (NSR) when adding.
In technique scheme, preferably, in described step D, the described nitrogen reductant sprayed in cooling section is the mixture of described urea and described bicarbonate of ammonia.It is the ratio of 2.5 to 3 that described urea follows ammonia nitrogen mol ratio (NSR) when adding, and it is the ratio of 2 to 2.5 that described bicarbonate of ammonia follows ammonia nitrogen mol ratio (NSR) when adding.
In technique scheme, preferably, described stock oil comprises aromatic hydrocarbon, petroleum hydrocarbon or aliphatic saturated hydrocarbon.
The manufacture of carbon black is exactly high-temperature gas and high-temperature fuel oil firing, form the high temperature of more than 1700 DEG C, then stock oil scission reaction at this temperature, because high-temperature gas and high-temperature fuel oil all contain some impurity, the tail gas produced when manufacturing carbon black can contain oxynitride, oxysulfide, oxycarbide etc., in modern industry, general tail gas generates heat, generating etc., utilization for carbon black tail gas mainly utilizes carbon oxides, generally all can carry out desulfurization work and not carry out denitrogenation work before carrying out waste gas utilization.But oxynitride is also a kind of very strong pollutent, go to bring infringement to environment once be discharged in air.Present method is that a kind of directly carrying out after pelletizing of carbon black terminates dryly utilizes the reaction of nitrogen oxides of nitrogen reductant directly and in tail gas constantly, oxynitride and nitrogen reductant are reacted and generates nitrogen, water, use different nitrogen reductants sometimes also can produce carbonic acid gas or carbon monoxide.During existing denitrogenation processing, because temperature of reaction is not usually only at 300 DEG C-400 DEG C, a large amount of metal catalysts is needed to carry out denitrogenation, with high costs, inefficiency.And our rule directly carries out decarburization in the dry manufacturing stage of carbon black pellet, because drying temperature is between 1000 DEG C to 1200 DEG C, exhaust temperature is more than 800 DEG C, the reductive agent of nitrogen can be directly used to carry out denitrogenation like this, the reductive agent mainly ammoniacal liquor of nitrogen, urea and bicarbonate of ammonia, these reductive agents at high temperature can directly and reaction of nitrogen oxides without the need to other catalyzer, reduction ratio is high simultaneously, more than 80%, the mainly nitrogen G&W generated, environmentally safe, partial reduction agent also can generate carbonic acid gas and carbon monoxide, this kind of carbon class material can improve the utilising efficiency of tail gas.Extremely low by amount of nitrogen oxides in the produced carbon black tail gas of present method, substantially on environment without impact, be a kind of environment protection method producing carbon black, meet current social attaching importance to environmental protection main flow consciousness.
Compared with prior art, the present invention can carry out denitrogenation processing at the drying stage of carbon black pellet to tail gas, does not affect the drying of carbon black pellet simultaneously, make the conversion of nitrogen oxides in tail gas be nitrogen, reduce the pollution substance in tail gas.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1: the high temperature air that temperature reaches 800 DEG C after preheating reacts with the combustion oil after preheating and mixes, burns in Reaktionsofen, produce temperature at the hot combustion gas stream of about 1960 DEG C, hot combustion gas stream flows into and in trunnion, to spray into temperature after trunnion between 170 DEG C and the aromatic hydrocarbon of atomization, aromatic hydrocarbon mixes with hot combustion gas stream at reaction furnace chamber, rapid cracking, produces carbon black smoke.Carbon black smoke, after entering cooling section, sprays water coolant in cooling section, and carbon black smoke temperature after over-quenching drops to 950 DEG C, and carbon black smoke enters into air preheater and oil preheater after leaving from cooling section successively; Carbon black smoke makes carbon black smoke be separated into carbon black powder and high-temperature tail gas from entering carbon black grading device after oil preheater leaves, carbon black powder becomes carbon black pellet after prilling granulator, after carbon black pellet puts into the kiln of drying installation, high-temperature tail gas enters the kiln of drying installation simultaneously and flows to tail gas air flue, the drying temperature of kiln when drying is between 1000 DEG C to 1200 DEG C, in tail gas air flue, spray ammoniacal liquor when high-temperature tail gas cools to 950 DEG C in tail gas air flue, the ammonia vol of injection needs the ratio following ammonia nitrogen mol ratio (NSR) 1.5.Ammoniacal liquor can and high-temperature tail gas in oxynitride generation reduction reaction, the product of reaction is nitrogen G&W.HN 950 DEG C time
3to the reduction ratio of oxynitride 52.7%, then along with the reduction reduction ratio of temperature raises, until 740 DEG C reach reduction ratio peak value 84.3%, the reduction ratio 77.3% when then dropping to 700 DEG C.High-temperature tail gas in tail gas air flue from kiln out after temperature more than 1000 DEG C, then high-temperature tail gas temperature declines gradually in tail gas air flue, from tail gas air flue out time at about 700 DEG C, HN
3large with the temperature range of oxynitride generation reduction reaction, can react with high-temperature tail gas in tail gas air flue always, and add ammoniacal liquor 950 DEG C time, ammoniacal liquor can be allowed fully to react, add the reaction that ammoniacal liquor causes when preventing low temperature incomplete, tail gas has the phenomenon of residual ammonia.High-temperature tail gas from tail gas air flue out after, the oxynitride in high-temperature tail gas is reduced substantially, does not have ammonia simultaneously and remains, directly can carry out second stage employ.
Embodiment 2: the high temperature air that temperature reaches 800 DEG C after preheating reacts with the combustion oil after preheating and mixes, burns in Reaktionsofen, produce temperature at the hot combustion gas stream of about 1960 DEG C, hot combustion gas stream flows into and in trunnion, to spray into temperature after trunnion between 180 DEG C and the petroleum hydrocarbon of atomization, petroleum hydrocarbon mixes with hot combustion gas stream at reaction furnace chamber, rapid cracking, produces carbon black smoke.Carbon black smoke, after entering cooling section, sprays water coolant in cooling section, and carbon black smoke temperature after over-quenching drops to 950 DEG C, and carbon black smoke enters into air preheater and oil preheater after leaving from cooling section successively, carbon black smoke makes carbon black smoke be separated into carbon black powder and high-temperature tail gas from entering carbon black grading device after oil preheater leaves, carbon black powder becomes carbon black pellet after prilling granulator, after carbon black pellet puts into the kiln of drying installation, high-temperature tail gas enters the kiln of drying installation simultaneously and flows to tail gas air flue, the drying temperature of kiln when drying is between 1000 DEG C to 1200 DEG C, in tail gas air flue, ammoniacal liquor and bicarbonate mixture is sprayed when high-temperature tail gas cools to 950 DEG C in tail gas air flue, wherein ammonia vol needs the ratio following ammonia nitrogen mol ratio (NSR) 1.5, the bicarbonate of ammonia amount of spraying needs the ratio following ammonia nitrogen mol ratio (NSR) 2 to 2.5.The mixture of ammoniacal liquor and bicarbonate of ammonia can and high-temperature tail gas in oxynitride generation reduction reaction, the product of reaction is nitrogen G&W and oxycarbide.HN 950 DEG C time
3to the reduction ratio of oxynitride 52.7%, then along with the reduction reduction ratio of temperature raises, until 740 DEG C reach reduction ratio peak value 84.3%, the reduction ratio 77.3% when then dropping to 700 DEG C.Bicarbonate of ammonia between 800 DEG C to 900 DEG C to the reduction ratio of oxynitride between 84%-86%, 800 DEG C decline later rapidly, by the common reduction of ammoniacal liquor and bicarbonate of ammonia, bicarbonate of ammonia is good at high-temperature section denitrification effect, ammoniacal liquor is good at low temperature section denitrification effect, and reduction of nitrogen oxide can be made so more abundant.High-temperature tail gas in tail gas air flue from kiln out after temperature more than 1000 DEG C, then high-temperature tail gas temperature declines gradually in tail gas air flue, from tail gas air flue out time at about 700 DEG C, after the reaction on this road, oxynitride in carbon black smoke is reduced substantially, ammoniacal liquor and bicarbonate of ammonia react completely and can not remain simultaneously, and the new material produced is mainly CO, CO
2, these gases are main components of tail gas, are also that tail gas can the essential substance of second stage employ.
Embodiment 3: the high temperature air that temperature reaches 800 DEG C after preheating reacts with the combustion oil after preheating and mixes, burns in Reaktionsofen, produce temperature at the hot combustion gas stream of about 1960 DEG C, hot combustion gas stream flows into and in trunnion, to spray into temperature after trunnion between 190 DEG C and the aliphatic saturated hydrocarbon of atomization, aliphatic saturated hydrocarbon mixes with hot combustion gas stream at reaction furnace chamber, rapid cracking, produces carbon black smoke.Carbon black smoke, after entering cooling section, sprays water coolant in cooling section, and carbon black smoke temperature after over-quenching drops to 950 DEG C, and carbon black smoke enters into air preheater and oil preheater after leaving from cooling section successively; Carbon black smoke makes carbon black smoke be separated into carbon black powder and high-temperature tail gas from entering carbon black grading device after oil preheater leaves, carbon black powder becomes carbon black pellet after prilling granulator, after carbon black pellet puts into the kiln of drying installation, high-temperature tail gas enters the kiln of drying installation simultaneously and flows to tail gas air flue, the drying temperature of kiln when drying, between 1000 DEG C to 1200 DEG C, sprays the mixture of urea and bicarbonate of ammonia when high-temperature tail gas cools to 950 DEG C in tail gas air flue.The ammonia vol sprayed needs the ratio following ammonia nitrogen mol ratio (NSR) 2.5 to 3, and the bicarbonate of ammonia amount of injection needs the ratio following ammonia nitrogen mol ratio (NSR) 2 to 2.5.The mixture of urea and bicarbonate of ammonia can and high-temperature tail gas in oxynitride generation reduction reaction, the product of reaction is nitrogen G&W and oxycarbide.Urea about 900 DEG C time to the reduction ratio of oxynitride more than 86%, bicarbonate of ammonia between 800 DEG C to 900 DEG C to the reduction ratio of oxynitride between 84%-86%, 800 DEG C decline later rapidly, due to high-temperature tail gas in tail gas air flue can holding temperature more than 850 DEG C for a long time, so be used in the bicarbonate of ammonia of the good urea of this temperature denitrification effect.High-temperature tail gas in tail gas air flue from kiln out after temperature more than 1000 DEG C, then high-temperature tail gas temperature declines gradually in tail gas air flue, from tail gas air flue out time at about 700 DEG C, after the reaction on this road, oxynitride in high-temperature tail gas is reduced substantially, urea and bicarbonate of ammonia react completely and can not remain simultaneously, directly can carry out second stage employ.
Claims (7)
1. produce the novel environment friendly technique of carbon black for one kind, need to utilize reaction unit, primary heater unit and prilling granulator, reaction unit comprises Reaktionsofen, trunnion, reaction chamber and cooling section, primary heater unit comprises air preheater and oil preheater, prilling granulator comprises carbon black grading device, prilling granulator and drying installation, described drying installation comprises kiln and tail gas air flue, it is characterized in that comprising following step: steps A): the high temperature air that temperature reaches 750 DEG C to 900 DEG C after preheating reacts with the combustion oil after preheating and mixes in Reaktionsofen, burning, produce the hot combustion gas stream of temperature between 1700 DEG C to 2010 DEG C, hot combustion gas stream flows into and in trunnion, to spray into temperature after trunnion between 170 DEG C to 190 DEG C and the stock oil of atomization, stock oil mixes with hot combustion gas stream at reaction furnace chamber, rapid cracking, produce carbon black smoke, step B): carbon black smoke, after entering cooling section, sprays water coolant in cooling section, and carbon black smoke temperature after over-quenching drops to 950 DEG C, step C): carbon black smoke after leaving from cooling section successively to air preheater and oil preheater, step D): carbon black smoke makes carbon black smoke be separated into carbon black powder and high-temperature tail gas from entering carbon black grading device after oil preheater leaves, carbon black powder becomes carbon black pellet after prilling granulator, after carbon black pellet puts into the kiln of drying installation, high-temperature tail gas enters the kiln of drying installation simultaneously and flows to tail gas air flue, the drying temperature of kiln when drying, between 1000 DEG C to 1200 DEG C, adds nitrogen reductant when high-temperature tail gas cools to 950 DEG C in tail gas air flue in tail gas air flue.
2. a kind of novel environment friendly technique of producing carbon black according to claim 1, it is characterized by, described nitrogen reductant comprises ammoniacal liquor, urea and bicarbonate of ammonia.
3. a kind of novel environment friendly technique of producing carbon black according to claim 2, it is characterized by, in described step D, the described nitrogen reductant sprayed in cooling section is described ammoniacal liquor, and it is the ratio of 1.5 that described ammoniacal liquor follows ammonia nitrogen mol ratio (NSR) when adding.
4. a kind of novel environment friendly technique of producing carbon black according to claim 2, it is characterized by, in described step D, the described nitrogen reductant sprayed in cooling section is the mixture of described ammoniacal liquor and described bicarbonate of ammonia, it is the ratio of 1.5 that described ammoniacal liquor follows ammonia nitrogen mol ratio (NSR) when adding, and it is the ratio of 2 to 2.5 that described bicarbonate of ammonia follows ammonia nitrogen mol ratio (NSR) when adding.
5. a kind of novel environment friendly technique of producing carbon black according to claim 2, is characterized by, and in described step D, the described nitrogen reductant sprayed in cooling section is the mixture of described urea and described bicarbonate of ammonia.
6. it is the ratio of 2.5 to 3 that urea described in follows ammonia nitrogen mol ratio (NSR) when adding, and it is the ratio of 2 to 2.5 that described bicarbonate of ammonia follows ammonia nitrogen mol ratio (NSR) when adding.
7. a kind of novel environment friendly technique of producing carbon black according to claim 1, it is characterized by, described stock oil comprises aromatic hydrocarbon, petroleum hydrocarbon or aliphatic saturated hydrocarbon.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107033631A (en) * | 2017-05-11 | 2017-08-11 | 丰城黑豹炭黑有限公司 | The production method and product of a kind of chemical fibre colour carbon black |
| CN108659579A (en) * | 2018-07-20 | 2018-10-16 | 宁波德泰化学有限公司 | A kind of manufacturing method of environmentally-friecarbon carbon black |
| CN108774415A (en) * | 2018-07-20 | 2018-11-09 | 宁波德泰化学有限公司 | A kind of manufacturing method of energy conservation and environmental protection carbon black |
| CN114788989A (en) * | 2022-04-25 | 2022-07-26 | 光大绿色环保管理（深圳）有限公司 | Equipment and method suitable for whole-plant flue gas purification of waste tire treatment |
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| CN102977643A (en) * | 2012-12-09 | 2013-03-20 | 龙星化工股份有限公司 | Mixing easily-dispersable intermediate super wear-resisting carbon black and production process thereof |
| CN103338840A (en) * | 2010-11-12 | 2013-10-02 | 卡博特公司 | Method and apparatus for reducing NOx emissions in the incineration of tail gas |
| CN103506318A (en) * | 2013-09-29 | 2014-01-15 | 宁波德泰化学有限公司 | Carbon black and preparation device |
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| CN103338840A (en) * | 2010-11-12 | 2013-10-02 | 卡博特公司 | Method and apparatus for reducing NOx emissions in the incineration of tail gas |
| CN102977643A (en) * | 2012-12-09 | 2013-03-20 | 龙星化工股份有限公司 | Mixing easily-dispersable intermediate super wear-resisting carbon black and production process thereof |
| CN103506318A (en) * | 2013-09-29 | 2014-01-15 | 宁波德泰化学有限公司 | Carbon black and preparation device |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107033631A (en) * | 2017-05-11 | 2017-08-11 | 丰城黑豹炭黑有限公司 | The production method and product of a kind of chemical fibre colour carbon black |
| CN108659579A (en) * | 2018-07-20 | 2018-10-16 | 宁波德泰化学有限公司 | A kind of manufacturing method of environmentally-friecarbon carbon black |
| CN108774415A (en) * | 2018-07-20 | 2018-11-09 | 宁波德泰化学有限公司 | A kind of manufacturing method of energy conservation and environmental protection carbon black |
| CN114788989A (en) * | 2022-04-25 | 2022-07-26 | 光大绿色环保管理（深圳）有限公司 | Equipment and method suitable for whole-plant flue gas purification of waste tire treatment |
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